Water-insoluble azo dyestuffs and fiber dyed therewith



Patented Sept. 19, 1933 UNITED STATES PATENT OFFICE WATER-INSOLUBLE AZO DYESTUFFS AN FIBER DYED, THEREWITH Erwin Hofia and Erwin Thoma, Frankfort-onthe-Main-Hochst, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application March 6, 1929, Serial No. 344,915, and in Germany March 10, 1928 Claims. (Cl. 260-495) v Eel wherein the aryl radical may-be substituted or not, but must not contain-any group which renders the dyestuffs soluble in water, such as the sulfonic or carboxylic acid group. These compounds are obtainable by coupling diazotized 1- amino-Z- methyl-4 alkoxy 3.5- dihalogen ben- Zenes with an arylamide of the zfi hydroxy naph- 22 thoic acid and they can be produced in substance as well as on the fiber or on a substratum.

The new dyestuifs are remarkable for their properties as to general fastness; they are distinguished in particular byan excellent fastness 12,5; to washing-and to chlorine and many of them,

besides being very fast to kier-boiling, answer high requirements inrespecttofastness to light so that the use of the l-amino-2-methyl-4,-al-

koxy-3.5-dihalogen benzenes as diazo components constitutes an important progress in the manufacture of highly valuabe dyestuffs.

The 1-amino-2-methyl-4=-alko,xy-3.5-dihalogen benzenes are obtainable, for instance, by halogenating the 1-nitro-2-methyl-4-alkoxy benzenes and reducing the halogenation product with, for instance, iron and a small quantity of hydrochloricacid. i

The following examples serve to illustrate the invention but are not intended to limit it thereto, the parts being by weight: V i

(1) Cotton yarn is impregnated in known manner with a grounding liquor prepared as follows: 5 parts of 2-hydroxynaphthalene-3-carboxylic acid -.pv-s n aphthyl ami de, 1 5, parts of caustic soda solution'of 28% strength, 5 parts of formaldehyde of 40% strength and 10 partsof Turkey red oil of strength are dissolved in 500 parts of boiling water and the whole is made up with water to 1000'parts; The dyeing is then nitrite. The whole is made up to 1000 parts and developed in a diazo solution obtained in the folsodium acetate is added until the solution shows a neutral reaction to Congo paper. The dyed-V material, after being washed and soaped at boillng temperature, shows a bluish bright-red tint andpossesses an excellent fastness to kier-bc'ail ing and to light. The dyestuff obtained accord ing to this example has. the following. formula:

CH3 o1 N N- V 0on3 oo n (2) Cotton yarn is impregnated in known ma n ner with a grounding liquor prepared as follows: 10 parts of 2-hydrox5/naphthalene-3 carboxylic acid -ocnaphthylamide, 21 parts of Turkey red oil of 50% strength, 39 parts of caustic soda solution of 28% strength are dissolved in 500 parts of boiling water and the'whole 'isthen made up to 1000 parts. "The dyeing is then developed in the diazo solution obtainable according toExample 1 and further treated-as indicated in Example 1. The dyed material, after being washed andsoaped at boiling temperature has a very bluish bright-red tintand possesses a Very good fastness to kier-boiling and an excellent fastnes s to light. The dyestuff obtained according to this example has the following formula:

(3) When using 2-hydroxynaphthalene-3-carboxylic acid 4'-chloro-2'-methyl-l-anilide there is obtained a scarlet dyeing of excellent fastness to kier-boiling and remarkable fastness to light. The dyestufi has the following formula:

The 1- amino -2- methyl 4- methoxy -3.5- dichlorobenzene, when being recrystallized from diluted alcohol, melts at 112 C. to 113 C. v

Dyestuifs similar to those described in Examples 1-3 are obtainable by using as diazo components 1- amino 2- methyl --4- meth0Xy-3.5-dibromobenzene or 1-amin0-2-methyl-4-methoxy- 3.5-dihalogen benzenes containing in 3-position and 5-position two halogen atoms different from one another. When using as diazo components instead of the said methoxy compounds the corresponding ethoxy compounds'there are also obtainable dyestuffs having properties similar to those of the dyestuifs referred to in the preceding examples. I

We claim:

1. Water-insoluble azo-dyestuffs of the general formula:

CH3 Hal N N Oalkyl OH 7 Hal OO-NH-R wherein R, represents a radical of the benzene .or naphthalene series which must not contain free sulfonic or carboxylic acid groups, forming yellowish-red to brownish-red and bluish-red powders and yielding when produced on the fiber dyeings of excellent fastness properties.

2. Water-insoluble azo-dyestuffs of the general formula:

CH3 Hal wherein R represents a radical of the benzene or naphthalene series which must not contain free sulphonic or carboxylic acid groups, forming yellowish-red to brownish-red and bluish-red powders and yielding when produced on the fiber dyeings of excellent fastness properties.

3. Water-insoluble azo-dyestuffs of the general formula:

OHa Hal Oa1ky1 oo- H-R wherein R represents a radical of the benzene or naphthalene series which must not contain free sulfonic or carboxylic acid groups, forming yellowish-red to brownish-red and bluish-red powders and yielding when produced on the fiber dyeings of excellent fastness properties.

4. Water-insoluble azo-dyestuffs of the general formula:

wherein R represents a radical of the benzene or naphthalene series which must not contain free sulfonic or carboxylic acid groups, forming yellowish-red to brownish-red and bluish-red powders and yielding when produced on e the fiber dyeings of excellent fastness properties.

5. Water-insoluble azo dyestuifs of the general formula:

115 OO.N H .naphtl1yl forming bluish-red powders and yielding when produced on the fiber dyeings of excellent fast- 1 o ness properties.

'7. Water-insoluble azo dyestuffs of the gen eral formula:

CH3 2 Cl 00. NH. naphthyl forming bluish-red powders and yielding when produced on the fiber dyeings of excellent fastness p'roperties. V

8. The water-insoluble azo dyestuif of the following formula:

oo.NH

forming a bluish-red powder and yielding when produced on the fiber bluish bright-red tints of an excellent fastness to kier-boiling and to light.

lowing formula:

9. The water-insoluble azo-dyestuff of the foldyeing of good fastness to kier-boiling and CH3 C1 OO. NH-

ish bright-red tint of a boiling and to light.

10. The water-insoluble azo-dyestuff of lowing formula:

yielding when produced good fastness to kierthe 01- on the fiber a scarlet light.

11. Fiber claim 1.

12. Fiber claim 2.

13. Fiber claim 3.

14. Fiber claim 4.

15. Fiber claim 5.

16. Fiber claim 6.

1'7. Fiber claim 7.

18. Fiber claim 8.

19. Fiber claim 9.

20. Fiber claim 10.

dyed with the dyestuffs claimed ERWIN HOFFA.

ERWIN THOMA.

claimed claimed claimed claimed claimed claimed claimed claimed claimed 

